JP6781863B1 - New carbamic acid ester compound and acrylic rubber composition containing it - Google Patents
New carbamic acid ester compound and acrylic rubber composition containing it Download PDFInfo
- Publication number
- JP6781863B1 JP6781863B1 JP2020535273A JP2020535273A JP6781863B1 JP 6781863 B1 JP6781863 B1 JP 6781863B1 JP 2020535273 A JP2020535273 A JP 2020535273A JP 2020535273 A JP2020535273 A JP 2020535273A JP 6781863 B1 JP6781863 B1 JP 6781863B1
- Authority
- JP
- Japan
- Prior art keywords
- acrylic rubber
- weight
- vulcanization
- acid ester
- carbamic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- -1 carbamic acid ester compound Chemical class 0.000 title claims abstract description 53
- 229920000800 acrylic rubber Polymers 0.000 title claims abstract description 40
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 40
- 239000000203 mixture Substances 0.000 title claims description 28
- 238000004073 vulcanization Methods 0.000 claims abstract description 86
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 16
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 11
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 7
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 7
- 235000012438 extruded product Nutrition 0.000 claims 1
- 230000001629 suppression Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 25
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 24
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 23
- 239000000047 product Substances 0.000 description 18
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 15
- OPNUROKCUBTKLF-UHFFFAOYSA-N 1,2-bis(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N\C(N)=N\C1=CC=CC=C1C OPNUROKCUBTKLF-UHFFFAOYSA-N 0.000 description 14
- 238000000465 moulding Methods 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 229940126062 Compound A Drugs 0.000 description 9
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000006835 compression Effects 0.000 description 9
- 238000007906 compression Methods 0.000 description 9
- 230000008602 contraction Effects 0.000 description 9
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 8
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 150000004984 aromatic diamines Chemical class 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 description 5
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 5
- 229960002447 thiram Drugs 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- 235000002597 Solanum melongena Nutrition 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 241001441571 Hiodontidae Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000003606 tin compounds Chemical class 0.000 description 3
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 3
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical compound CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 description 2
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- GOVXKUCVZUROAN-UHFFFAOYSA-N CCc1c[nH]c2c1cccc2 Chemical compound CCc1c[nH]c2c1cccc2 GOVXKUCVZUROAN-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 150000003755 zirconium compounds Chemical class 0.000 description 2
- BHGUSWOZYFZTMG-UHFFFAOYSA-N (1-methylpyrrol-2-yl)methanol Chemical compound CN1C=CC=C1CO BHGUSWOZYFZTMG-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- UTOVMEACOLCUCK-SNAWJCMRSA-N (e)-4-butoxy-4-oxobut-2-enoic acid Chemical compound CCCCOC(=O)\C=C\C(O)=O UTOVMEACOLCUCK-SNAWJCMRSA-N 0.000 description 1
- XLYMOEINVGRTEX-ONEGZZNKSA-N (e)-4-ethoxy-4-oxobut-2-enoic acid Chemical compound CCOC(=O)\C=C\C(O)=O XLYMOEINVGRTEX-ONEGZZNKSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 1
- GIMDPFBLSKQRNP-UHFFFAOYSA-N 1,1-diphenylethanol Chemical compound C=1C=CC=CC=1C(O)(C)C1=CC=CC=C1 GIMDPFBLSKQRNP-UHFFFAOYSA-N 0.000 description 1
- FUPAJKKAHDLPAZ-UHFFFAOYSA-N 1,2,3-triphenylguanidine Chemical compound C=1C=CC=CC=1NC(=NC=1C=CC=CC=1)NC1=CC=CC=C1 FUPAJKKAHDLPAZ-UHFFFAOYSA-N 0.000 description 1
- TUPIWWRTTIRPDS-UHFFFAOYSA-N 1,2-bis(hydroxymethyl)guanidine Chemical compound OCNC(=N)NCO TUPIWWRTTIRPDS-UHFFFAOYSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- HILAYQUKKYWPJW-UHFFFAOYSA-N 1-dodecylguanidine Chemical compound CCCCCCCCCCCCN=C(N)N HILAYQUKKYWPJW-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- XEEANGGQJOWRTG-UHFFFAOYSA-N 1h-indol-2-ylmethanol Chemical compound C1=CC=C2NC(CO)=CC2=C1 XEEANGGQJOWRTG-UHFFFAOYSA-N 0.000 description 1
- XSQHUYDRSDBCHN-UHFFFAOYSA-N 2,3-dimethyl-2-propan-2-ylbutanenitrile Chemical compound CC(C)C(C)(C#N)C(C)C XSQHUYDRSDBCHN-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- MBEVSMZJMIQVBG-UHFFFAOYSA-N 2-(hydroxymethyl)guanidine Chemical compound NC(N)=NCO MBEVSMZJMIQVBG-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 1
- PTJDGKYFJYEAOK-UHFFFAOYSA-N 2-butoxyethyl prop-2-enoate Chemical compound CCCCOCCOC(=O)C=C PTJDGKYFJYEAOK-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- PARCMDAOZHNXLU-UHFFFAOYSA-N 2-ethylhexanoic acid;tin Chemical compound [Sn].CCCCC(CC)C(O)=O.CCCCC(CC)C(O)=O PARCMDAOZHNXLU-UHFFFAOYSA-N 0.000 description 1
- NWIIFBPIDORBCY-UHFFFAOYSA-N 2-methylprop-2-enoic acid;propane-1,2,3-triol;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(=C)C(O)=O.OCC(O)CO NWIIFBPIDORBCY-UHFFFAOYSA-N 0.000 description 1
- QRJZGVVKGFIGLI-UHFFFAOYSA-N 2-phenylguanidine Chemical compound NC(=N)NC1=CC=CC=C1 QRJZGVVKGFIGLI-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- LAIUFBWHERIJIH-UHFFFAOYSA-N 3-Methylheptane Chemical class CCCCC(C)CC LAIUFBWHERIJIH-UHFFFAOYSA-N 0.000 description 1
- UACBZRBYLSMNGV-UHFFFAOYSA-N 3-ethoxypropyl prop-2-enoate Chemical compound CCOCCCOC(=O)C=C UACBZRBYLSMNGV-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- XNCOSPRUTUOJCJ-UHFFFAOYSA-N Biguanide Chemical compound NC(N)=NC(N)=N XNCOSPRUTUOJCJ-UHFFFAOYSA-N 0.000 description 1
- 229940123208 Biguanide Drugs 0.000 description 1
- QGRPEBYUVHSYDR-UHFFFAOYSA-N CC(=C)C(O)=O.OCC(O)COOC(=O)C=C Chemical compound CC(=C)C(O)=O.OCC(O)COOC(=O)C=C QGRPEBYUVHSYDR-UHFFFAOYSA-N 0.000 description 1
- 0 CC(C)(c1ccccc1)O* Chemical compound CC(C)(c1ccccc1)O* 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- SQSPRWMERUQXNE-UHFFFAOYSA-N Guanylurea Chemical compound NC(=N)NC(N)=O SQSPRWMERUQXNE-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- GSCCALZHGUWNJW-UHFFFAOYSA-N N-Cyclohexyl-N-methylcyclohexanamine Chemical compound C1CCCCC1N(C)C1CCCCC1 GSCCALZHGUWNJW-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 102100030090 Probable ATP-dependent RNA helicase DHX58 Human genes 0.000 description 1
- 101710144666 Probable ATP-dependent RNA helicase DHX58 Proteins 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- LINDOXZENKYESA-UHFFFAOYSA-N TMG Natural products CNC(N)=NC LINDOXZENKYESA-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- HAMNKKUPIHEESI-UHFFFAOYSA-N aminoguanidine Chemical compound NNC(N)=N HAMNKKUPIHEESI-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- NIVZHWNOUVJHKV-UHFFFAOYSA-N bethanidine Chemical compound CN\C(=N/C)NCC1=CC=CC=C1 NIVZHWNOUVJHKV-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- AGVAZMGAQJOSFJ-WZHZPDAFSA-M cobalt(2+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(1r,2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2 Chemical compound [Co+2].N#[C-].[N-]([C@@H]1[C@H](CC(N)=O)[C@@]2(C)CCC(=O)NC[C@@H](C)OP(O)(=O)O[C@H]3[C@H]([C@H](O[C@@H]3CO)N3C4=CC(C)=C(C)C=C4N=C3)O)\C2=C(C)/C([C@H](C\2(C)C)CCC(N)=O)=N/C/2=C\C([C@H]([C@@]/2(CC(N)=O)C)CCC(N)=O)=N\C\2=C(C)/C2=N[C@]1(C)[C@@](C)(CC(N)=O)[C@@H]2CCC(N)=O AGVAZMGAQJOSFJ-WZHZPDAFSA-M 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 229940126534 drug product Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 229940093858 ethyl acetoacetate Drugs 0.000 description 1
- 229920006229 ethylene acrylic elastomer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- SINFYWWJOCXYFD-UHFFFAOYSA-N methoxymethyl prop-2-enoate Chemical compound COCOC(=O)C=C SINFYWWJOCXYFD-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
- B29C39/003—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C271/12—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/333—Radicals substituted by oxygen or sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D209/12—Radicals substituted by oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/205—Compounds containing groups, e.g. carbamates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3462—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L13/00—Compositions of rubbers containing carboxyl groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2019/00—Use of rubber not provided for in a single one of main groups B29K2007/00 - B29K2011/00, as moulding material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pyrrole Compounds (AREA)
- Indole Compounds (AREA)
Abstract
一般式Z-OCONH(CH2)nNHCOO-Z 〔Ｉ〕ここで、Zは下記〔i〕、〔ii〕または〔iii〕であり、nは2〜10の整数である(ここで、R1およびR2はそれぞれ独立に炭素数1〜5の低級アルキル基であり、R3は水素原子または炭素数1〜5の低級アルキル基であり、aは1または2である)で表わされるカルバミン酸エステル化合物。このカルバミン酸エステル化合物は、カルボキシル基含有アクリルゴムの加硫剤として用いられ、スコーチ抑制による加硫速度の遅延を改善する。General formula Z-OCONH (CH2) nNHCOO-Z [I] where Z is the following [i], [ii] or [iii], and n is an integer from 2 to 10 (where R1 and R2). Are independently lower alkyl groups with 1 to 5 carbon atoms, R3 is a hydrogen atom or lower alkyl group with 1 to 5 carbon atoms, and a is 1 or 2). This carbamic acid ester compound is used as a vulcanizing agent for carboxyl group-containing acrylic rubber, and improves the delay in vulcanization rate due to scorch suppression.
Description
本発明は、新規カルバミン酸エステル化合物およびそれを含有するアクリルゴム組成物に関する。さらに詳しくは、カルボキシル基含有アクリルゴム用の新規加硫剤として用いられるカルバミン酸エステル化合物およびそれを含有するアクリルゴム組成物に関する。 The present invention relates to a novel carbamic acid ester compound and an acrylic rubber composition containing the same. More specifically, the present invention relates to a carbamic acid ester compound used as a novel vulcanizing agent for a carboxyl group-containing acrylic rubber, and an acrylic rubber composition containing the same.
カルボキシル基含有アクリルゴムは、アクリルゴムの中でも特に耐熱性、耐圧縮永久歪特性にすぐれ、かつ金属への非腐食性、環境への配慮などがなされたハロゲン非含有アクリルゴムであるため、近年ホース、シール材用途等への需要が増えている。しかしながら、加硫速度に対してスコーチタイムが短く、すなわち加硫速度を速くすればスコーチタイムが短すぎ、加硫速度を遅くすればスコーチタイムは長くなるという傾向を有している。 Carboxylic group-containing acrylic rubber is a halogen-free acrylic rubber that has excellent heat resistance, compression set resistance, non-corrosion to metals, and environmental friendliness among acrylic rubbers. , Demand for sealing materials is increasing. However, there is a tendency that the scorch time is short with respect to the vulcanization rate, that is, the scorch time is too short when the vulcanization rate is increased, and the scorch time is long when the vulcanization rate is decreased.
より具体的には、加硫速度を満足し得る速さにまで高めた場合、スコーチタイムが短く、生地流れの悪化を招き、成形不良となる。加硫速度を遅くした場合には、成形時間が長くなり、コストの上昇につながる。このことは、加硫速度が速く、スコーチタイムが長いという理想からいうと、成形性に劣るということになる。 More specifically, when the vulcanization rate is increased to a satisfactory rate, the scorch time is short, the dough flow is deteriorated, and molding is defective. If the vulcanization rate is slowed down, the molding time becomes long, which leads to an increase in cost. This means that the moldability is inferior in terms of the ideal that the vulcanization rate is high and the scorch time is long.
アクリルゴムの加硫成形方法としては、一般に型成形(射出成形、圧縮成形、トランスファー成形等)と押出成形とが用いられており、現在は成形時の加硫速度とスコーチタイムとのバランスをとるために、下記２つの加硫系の流れがある。
(1) 脂肪族ジアミン(加硫剤)／グアニジン(加硫促進剤)
(2) 芳香族ジアミン(加硫剤)／グアニジン(加硫促進剤)
Mold molding (injection molding, compression molding, transfer molding, etc.) and extrusion molding are generally used as vulcanization molding methods for acrylic rubber, and currently, the vulcanization rate at the time of molding and the scorch time are balanced. Therefore, there are the following two vulcanization system flows.
(1) Aliphatic diamine (vulcanization agent) / guanidine (vulcanization accelerator)
(2) Aromatic diamine (vulcanization agent) / guanidine (vulcanization accelerator)
主に加硫速度を優先する金型成形用途に用いられる脂肪族ジアミン加硫系は、主にスコーチタイム(t5：10分以上)を優先する押出成形用途の芳香族ジアミン加硫系よりも、加硫速度は速いがスコーチタイムが短く、一方脂肪族ジアミン加硫系よりもスコーチタイムが長い芳香族ジアミン加硫系(加硫剤としては4,4′-ジアミノジフェニルエーテル、2,2-ビス〔4-(4-アミノフェノキシ)フェニル〕プロパン、メチレンジアニリン等が用いられる)は、加硫速度が遅いといった欠点がみられる。したがって、高速加硫を可能とし、かつ非スコーチを両立することができる加硫系が望まれている。 The aliphatic diamine vulcanization system mainly used for mold molding where the vulcanization rate is prioritized is higher than the aromatic diamine vulcanization system for extrusion molding which mainly prioritizes scorch time (t5: 10 minutes or more). Aromatic diamine vulcanization system (4,4'-diaminodiphenyl ether, 2,2-bis [as a vulcanizing agent], which has a high vulcanization rate but a short scorch time, while has a longer scorch time than an aliphatic diamine vulcanization system. 4- (4-Aminophenoxy) phenyl] propane, methylenedianiline, etc.) has the drawback of slow vulcanization rate. Therefore, a vulcanization system that enables high-speed vulcanization and is compatible with non-scorch is desired.
ここで、脂肪族ジアミン加硫系の加硫機構について考えてみるに、脂肪族ジアミンとしてはヘキサメチレンジアミンカーバメート(6-アミノヘキシルカルバミン酸)H3N+(CH2)6NHCOO-がカルボキシル基含有アクリルゴムの加硫に広く用いられており、その加硫反応はこの加硫剤化合物に熱が適用されることで、ヘキサメチレンジアミンのアミノ基の保護基が100℃付近から熱分解脱炭酸してヘキサメチレンジアミンとなり、アクリルゴム中の架橋性官能基であるカルボキシル基等と反応して、加硫反応が進行するという形をとっている。このため、スコーチタイムが短い(スコーチ安定性に劣る)という欠点を有する。また、ヘキサメチレンジアミンを炭酸塩としている理由の一つは、ヘキサメチレンジアミンは吸湿性が強くかつ気化し易いため、取扱いが困難であることによる。 Here, considering the vulcanization mechanism of the aliphatic diamine vulcanization system, hexamethylene diamine carbamate (6-aminohexyl carbamate) H 3 N + (CH 2 ) 6 NHCOO - is a carboxyl group as the aliphatic diamine. It is widely used for vulcanization of contained acrylic rubber, and in the vulcanization reaction, heat is applied to this vulcanizing agent compound, and the protective group of the amino group of hexamethylenediamine is thermally decomposed and decarbonized from around 100 ° C. Then, it becomes hexamethylenediamine, which reacts with a carboxyl group or the like which is a crosslinkable functional group in acrylic rubber, and the vulcanization reaction proceeds. Therefore, it has a drawback that the scorch time is short (the scorch stability is inferior). Further, one of the reasons why hexamethylenediamine is used as a carbonate is that hexamethylenediamine is difficult to handle because it has strong hygroscopicity and is easily vaporized.
なお、カルボキシル基含有アクリルゴムとしては、カルボキシル基含有エチレンアクリルゴム(デュポン社製品ベーマックG)、特定のカルボキシル基含有アクリルゴム(電気化学工業製品電化ER)等も含まれ、これらのカルボキシル基含有アクリルゴムについてもスコーチタイムが短いという問題がみられる。なお、特許文献１〜１０中には、加硫速度が速く、スコーチタイムも長くなるものもあるが、これらの場合には耐圧縮永久歪特性の低下を免れないものもある。 The carboxyl group-containing acrylic rubber includes a carboxyl group-containing ethylene acrylic rubber (DuPont product Bemac G), a specific carboxyl group-containing acrylic rubber (electrochemical industry product electrification ER), and the like, and these carboxyl group-containing acrylics. There is also a problem with rubber that the scorch time is short. In addition, in some of Patent Documents 1 to 10, the vulcanization rate is high and the scorch time is long, but in these cases, the compression set resistance is inevitably deteriorated.
また、本出願人の出願に係る特許文献１１には、HMDA-Fmoc
R1：C1〜C20の2価脂肪族アルキレン基
2価脂環式シクロアルキレン基
2価芳香族基
R2：カーバメート構造としたとき、塩基性加硫促進剤の作
用で分解し、促進剤の作用で分解し、ジアミンを発生
し得る基
n：0、1または2
m：0または1
で表わされるジウレタン化合物が記載されているが、後記比較例１０〜１１に記載される如く、tc10およびtc90の値が十分短いとはいえず、またME(MH-ML)の値が十分大きいとはいえない。
Further, in Patent Document 11 relating to the application of the present applicant, HMDA-Fmoc
R 1 : Divalent aliphatic alkylene group from C 1 to C 20
Divalent alicyclic cycloalkylene group
Divalent aromatic group
R 2 : Production of basic vulcanization accelerator when it has a carbamate structure
Decomposes by the action of the accelerator and generates diamine
Possible group
n: 0, 1 or 2
m: 0 or 1
Although the diurethane compound represented by is described, as described in Comparative Examples 10 to 11 described later, it cannot be said that the values of tc10 and tc90 are sufficiently short, and the values of ME (MH-ML) are sufficiently large. I can't say.
本発明の目的は、架橋性基含有アクリルゴム用の新規加硫剤として用いられるジウレタン化合物およびそれを加硫剤として含有し、スコーチ抑制による加硫速度の遅延を改善し、すなわち脂肪族ジアミンの有する良好な加硫速度および芳香族ジアミンの有する良好なスコーチ安定性を両立せしめたアクリルゴム組成物を提供することにある。 An object of the present invention is to improve the delay of the vulcanization rate due to scorch suppression by containing a diurethane compound used as a novel vulcanizing agent for crosslinkable group-containing acrylic rubber and the vulcanizing agent, that is, an aliphatic diamine. It is an object of the present invention to provide an acrylic rubber composition having both a good vulcanization rate and a good scorch stability of an aromatic diamine.
本発明によって、一般式
Z-OCONH(CH2)nNHCOO-Z 〔Ｉ〕
ここで、Zは下記〔i〕、〔ii〕または〔iii〕であり、nは2〜10の整数である
Z-OCONH (CH 2 ) n NHCOO-Z [I]
Where Z is the following [i], [ii] or [iii], and n is an integer from 2 to 10.
このカルバミン酸エステル化合物は、カルボキシル基含有アクリルゴムに加硫促進剤と共に配合され、アクリルゴム組成物を形成させる。 This carbamic acid ester compound is blended with a carboxyl group-containing acrylic rubber together with a vulcanization accelerator to form an acrylic rubber composition.
本発明に係る新規化合物であるカルバミン酸エステル化合物は、カルボキシル基含有アクリルゴムの加硫剤として好適であり、特にカルバミン酸エステル化合物および塩基性加硫促進剤を配合したカルボキシル基含有アクリルゴム組成物は、迅速な加硫速度および良好なスコーチ安定性を有し、従来のアミン加硫系では実現できなかった短時間射出成形などを可能とする。 The carbamic acid ester compound, which is a novel compound according to the present invention, is suitable as a vulcanizing agent for a carboxyl group-containing acrylic rubber, and in particular, a carboxyl group-containing acrylic rubber composition containing a carbamic acid ester compound and a basic vulcanization accelerator. Has a rapid vulcanization rate and good scorch stability, and enables short-time injection molding and the like, which could not be realized by a conventional amine vulcanization system.
また、スコーチの観点からみて、脂肪族ジアミン加硫系が使用できず芳香族ジアミン加硫系を使用していた押出成形用途の加硫成形においても、本発明のカルバミン酸エステル化合物との併用により、高速加硫(短時間加硫)および高温押出が可能となる。 Further, from the viewpoint of the scorch, even in the vulcanization molding for extrusion molding where the aliphatic diamine vulcanization system cannot be used and the aromatic diamine vulcanization system is used, the vulcanization molding for extrusion molding can be performed in combination with the carbamate ester compound of the present invention. , High speed vulcanization (short time vulcanization) and high temperature extrusion are possible.
このため、スコーチの抑制による加硫速度の遅延を改善することができ、射出成形時などに問題となっていたこの問題を解決することで、成形条件の設定範囲を広げることを可能としている。また、加硫物性、特に耐圧縮永久歪特性の大きな低下もみられない。その結果、射出成形、圧縮成形、トランスファー成形等の型成形のみならず、押出成形にも有効に適用することができ、オイルシール、ガスケット、Oリング等の各種シール類、ホース、ダイヤフラム、ロール、防振ゴム、工業用ゴム部品等の加硫成形に有効に用いることができる。 Therefore, it is possible to improve the delay of the vulcanization rate due to the suppression of the scorch, and by solving this problem which has been a problem at the time of injection molding, it is possible to expand the setting range of the molding conditions. In addition, there is no significant decrease in vulcanization properties, especially compression set resistance. As a result, it can be effectively applied not only to mold molding such as injection molding, compression molding and transfer molding, but also to extrusion molding, and various seals such as oil seals, gaskets and O-rings, hoses, diaphragms, rolls, etc. It can be effectively used for vulcanization molding of anti-vibration rubber, industrial rubber parts, etc.
一般式
Z-OCONH(CH2)nNHCOO-Z 〔Ｉ〕
ここでZは下記〔i〕、〔ii〕または〔iii〕であり、nは2〜10の整数、好ましくは6である。
Z-OCONH (CH 2 ) n NHCOO-Z [I]
Here, Z is the following [i], [ii] or [iii], and n is an integer of 2 to 10, preferably 6.
かかる置換基を有するカルバミン酸エステル化合物は、直鎖状アルキレンジイソシアネート ONC(CH2)nNCOと水酸基含有化合物であるインドリルメタノール、N-アルキル-2-ヒドロキシメチルピロールまたは一般式
具体的には、次のような反応によって製造される。
カルバミン酸エステル化合物および水酸基含有化合物とは、トルエン、ジオキサン、メチルエチルケトン等の有機溶媒中で約10〜120℃で反応させた後、不溶部をろ別することにより、それの製造が行われる。 The carbamic acid ester compound and the hydroxyl group-containing compound are produced by reacting them in an organic solvent such as toluene, dioxane, or methyl ethyl ketone at about 10 to 120 ° C., and then filtering the insoluble portion.
かかる反応は、ウレタン硬化触媒存在下で行うこともできる。ウレタン硬化触媒としては、有機スズ化合物、有機チタン化合物、有機ジルコニウム化合物または有機アミン化合物が挙げられ、有機アミン化合物と有機スズ化合物を併用することもでき、これらは直鎖状アルキレンジイソシアネート100重量部に対して約0.1〜10重量部の割合で用いられる。 Such a reaction can also be carried out in the presence of a urethane curing catalyst. Examples of the urethane curing catalyst include an organic tin compound, an organic titanium compound, an organic zirconium compound or an organic amine compound, and an organic amine compound and an organic tin compound can be used in combination, and these are 100 parts by weight of a linear alkylene diisocyanate. On the other hand, it is used at a ratio of about 0.1 to 10 parts by weight.
ウレタン硬化触媒として用いられる有機スズ化合物としては、例えばジラウリン酸ジブチルスズ、ビス(2-エチルヘキサン酸)スズ、ジブチルスズビス(2,4-ペンタンジオネート)等が、有機チタン化合物としては、例えばチタンジイソプロポキシビス(エチルアセトアセテート)等が、有機ジルコニウム化合物としては、例えばジルコニウムジブトキシビス(エチルアセトアセテート)、ジルコニウムテトラ(アセチルアセトネート)等が挙げられる。 Examples of the organic tin compound used as the urethane curing catalyst include dibutyltin dilaurate, bis (2-ethylhexanoic acid) tin, and dibutyltin bis (2,4-pentandionate), and examples of the organic titanium compound include titanium di. Isopropoxybis (ethylacetoacetate) and the like, and examples of the organic zirconium compound include zirconium dibutoxybis (ethylacetacetate) and zirconium tetra (acetylacetonate).
また、有機アミン化合物としては、トリエチレンジアミン、ビス(ジメチルアミノエチル)エーテル、1,4-ジアザビシクロ[2.2.2]オクタン、ペンタメチルジエチレントリアミン、N,N-ジメチルシクロヘキシルアミン、N-メチルジシクロヘキシルアミン、N,N,N,N-テトラメチルプロピレンジアミン、N,N,N,N-テトラメチルヘキサメチレンジアミン、N-メチルモルホリン、N-エチルモルホリン、N,N-ジメチルエタノールアミン、N,N-ジエチルエタノールアミン、1,8-ジアザビシクロ[5.4.0]ウンデセン-7またはその有機酸塩、1,5-ジアザビシクロ[4.3.0]ノネン-5等が挙げられる。1,8-ジアザビシクロ[5.4.0]ウンデセン-7の有機酸塩としては、例えば1,8-ジアザビシクロ[5.4.0]ウンデセン-7のギ酸塩、2-エチルヘキサン塩、フェノール塩、オクチル酸塩、ｐ−トルエンスルホン酸塩、o-フタル酸塩等が挙げられる。 Examples of the organic amine compound include triethylenediamine, bis (dimethylaminoethyl) ether, 1,4-diazabicyclo [2.2.2] octane, pentamethyldiethylenetriamine, N, N-dimethylcyclohexylamine, N-methyldicyclohexylamine, and N. , N, N, N-tetramethylpropylenediamine, N, N, N, N-tetramethylhexamethylenediamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine, N, N-diethylethanol Amine, 1,8-diazabicyclo [5.4.0] undecene-7 or an organic acid salt thereof, 1,5-diazabicyclo [4.3.0] nonen-5 and the like can be mentioned. Examples of the organic acid salt of 1,8-diazabicyclo [5.4.0] undecene-7 include formate of 1,8-diazabicyclo [5.4.0] undecene-7, 2-ethylhexane salt, phenol salt, and octylate. , P-Toluenesulfonate, o-phthalate and the like.
得られたカルバミン酸エステル化合物は、カルボキシル基含有アクリルゴムに加硫剤として配合され、アクリルゴム組成物を形成させる。 The obtained carbamic acid ester compound is blended with a carboxyl group-containing acrylic rubber as a vulcanizing agent to form an acrylic rubber composition.
カルボキシル基含有アクリルゴムとしては、炭素数1〜8のアルキル基を有するアルキルアクリレートおよび炭素数2〜8のアルコキシアルキル基を有するアルコキシアルキルアクリレートの少くとも１種類とカルボキシル基含有不飽和化合物とを共重合させたものが用いられる。 The carboxyl group-containing acrylic rubber includes at least one type of alkyl acrylate having an alkyl group having 1 to 8 carbon atoms and an alkoxyalkyl acrylate having an alkoxyalkyl group having 2 to 8 carbon atoms, and a carboxyl group-containing unsaturated compound. A polymerized product is used.
アルキルアクリレートとしては、例えばメチルアクリレート、エチルアクリレート、プロピルアクリレート、イソプロピルアクリレート、n-ブチルアクリレート、n-ヘキシルアクリレート、2-エチルヘキシルアクリレート、n-オクチルアクリレートおよびこれらに対応するメタクリレートが用いられる。一般的に、アルキル基の鎖長が長くなると耐寒性の点では有利となるが、耐油性では不利となり、鎖長が短いとその逆の傾向がみられ、耐油性、耐寒性のバランス上からはエチルアクリレート、n-ブチルアクリレートが好んで用いられる。 As the alkyl acrylate, for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate and the corresponding methacrylate are used. In general, a long chain length of an alkyl group is advantageous in terms of cold resistance, but it is disadvantageous in oil resistance, and a short chain length shows the opposite tendency, from the viewpoint of the balance between oil resistance and cold resistance. Ethyl acrylate and n-butyl acrylate are preferably used.
また、アルコキシアルキルアクリレートとしては、例えばメトキシメチルアクリレート、2-メトキシエチルアクリレート、2-エトキシエチルアクリレート、2-n-ブトキシエチルアクリレート、3-エトキシプロピルアクリレート等が用いられ、好ましくは2-メトキシエチルアクリレート、2-エトキシエチルアクリレートが用いられる。アルコキシアルキルアクリレートとアルキルアクリレートとは、それぞれ単独でも用いられるが、好ましくは前者が約60〜0重量％、また後者が約40〜100重量％の割合で用いられ、アルコキシアルキルアクリレートを共重合させた場合には耐油性と耐寒性のバランスが良好となり、ただしこれよりも多い割合で共重合させると常態物性と耐熱性が低下する傾向がみられるようになる。 As the alkoxyalkyl acrylate, for example, methoxymethyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-n-butoxyethyl acrylate, 3-ethoxypropyl acrylate and the like are used, and 2-methoxyethyl acrylate is preferable. , 2-ethoxyethyl acrylate is used. The alkoxyalkyl acrylate and the alkyl acrylate can be used alone, but preferably the former is used in a proportion of about 60 to 0% by weight and the latter is used in a proportion of about 40 to 100% by weight, and the alkoxyalkyl acrylate is copolymerized. In some cases, the balance between oil resistance and cold resistance is good, but if copolymerization is carried out at a higher ratio than this, the normal physical properties and heat resistance tend to decrease.
カルボキシル基含有不飽和化合物としては、マレイン酸またはフマル酸のメチル、エチル、プロピル、イソプロピル、n-ブチル、イソブチル等のモノアルキルエステル、イタコン酸またはシトラコン酸のメチル、エチル、プロピル、イソプロピル、n-ブチル、イソブチル等のモノアルキルエステル等が挙げられ、好ましくはマレイン酸モノn-ブチルエステル、フマル酸モノエチルエステル、フマル酸モノn-ブチルエステルが用いられる。これらのカルボキシル基含有不飽和化合物は、カルボキシル基含有アクリルエラストマー中約0.5〜10重量％、好ましくは約1〜7重量％を占めるような共重合割合で用いられ、これよりも少ない共重合割合では加硫が不十分となって圧縮永久歪値が悪化し、一方これよりも共重合割合を多くするとスコーチし易くなる。なお、共重合反応は、重合転化率が90％以上となるように行われるので、仕込み各単量体重量比がほぼ生成共重合体の共重合組成重量比となる。 Examples of the carboxyl group-containing unsaturated compound include monoalkyl esters such as methyl, ethyl, propyl, isopropyl, n-butyl and isobutyl of maleic acid or fumaric acid, and methyl, ethyl, propyl, isopropyl and n- of itaconic acid or citraconic acid. Examples thereof include monoalkyl esters such as butyl and isobutyl, and preferably, maleic acid mono-n-butyl ester, fumaric acid monoethyl ester, and fumaric acid mono n-butyl ester are used. These carboxyl group-containing unsaturated compounds are used in a copolymerization ratio such that they occupy about 0.5 to 10% by weight, preferably about 1 to 7% by weight of the carboxyl group-containing acrylic elastomer, and at a lower copolymerization ratio. Insufficient vulcanization results in deterioration of the compression set, while increasing the copolymerization ratio makes scorch easier. Since the copolymerization reaction is carried out so that the polymerization conversion rate is 90% or more, the weight ratio of each charged monomer is substantially the copolymerization composition weight ratio of the produced copolymer.
カルボキシル基含有アクリルエラストマー中には、さらに他の共重合可能なエチレン性不飽和単量体、例えばスチレン、α-メチルスチレン、ビニルトルエン、ビニルナフタレン、アクリロニトリル、メタクリロニトリル、アクリル酸アミド、酢酸ビニル、シクロヘキシルアクリレート、ベンジルアクリレート、エチレン、プロピレン、ピペリレン、ブタジエン、イソプレン、ペンタジエン等を、約50重量％以下の割合で共重合させることができる。 Among the carboxyl group-containing acrylic elastomers are still other copolymerizable ethylenically unsaturated monomers such as styrene, α-methylstyrene, vinyltoluene, vinylnaphthalene, acrylonitrile, methacrylonitrile, acrylic acid amide, vinyl acetate. , Cyclohexyl acrylate, benzyl acrylate, ethylene, propylene, piperylene, butadiene, isoprene, pentadiene and the like can be copolymerized at a ratio of about 50% by weight or less.
さらに、必要に応じて、混練加工性や押出加工性などを改善する目的で、多官能性(メタ)アクリレートまたはオリゴマー、例えばエチレングリコール、プロピレングリコール、1,4-ブタンジオール、1,6-ヘキサンジオール、1,9-ノナンジオール等のアルキレングリコールのジ(メタ)アクリレート、ネオペンチルグリコール、テトラエチレングリコール、トリプロピレングリコール、ポリプロピレングリコール等のジ(メタ)アクリレート、ビスフェノールA・エチレンオキサイド付加物ジアクリレート、ジメチロールトリシクロデカンジアクリレート、グリセリンメタクリレートアクリレート、3-アクリロイルオキシグリセリンモノメタクリレート等をさらに共重合して用いることもできる。ここで、(メタ)アクリレートは、アクリレートまたはメタクリレートを指している。 Further, if necessary, polyfunctional (meth) acrylates or oligomers such as ethylene glycol, propylene glycol, 1,4-butanediol, and 1,6-hexane are used for the purpose of improving kneading processability and extrusion processability. Di (meth) acrylate of alkylene glycol such as diol and 1,9-nonanediol, di (meth) acrylate of alkylene glycol such as neopentyl glycol, tetraethylene glycol, tripropylene glycol and polypropylene glycol, bisphenol A / ethylene oxide adduct diacrylate , Dimethyloltricyclodecanediacrylate, glycerin methacrylate acrylate, 3-acryloyloxyglycerin monomethacrylate and the like can be further copolymerized and used. Here, (meth) acrylate refers to acrylate or methacrylate.
加硫剤としてのカルバミン酸エステル化合物は、カルボキシル基含有アクリルエラストマー100重量部当り、約0.1〜10重量部、好ましくは約0.5〜5重量部の割合で用いられる。この加硫剤の使用割合がこれよりも少ないと、加硫が不十分となり、引張強さ、圧縮永久歪などの点で十分な物性が得られない。一方、これよりも多い割合で用いられると、破断時伸びの低下や圧縮永久歪の悪化を招くようになる。 The carbamic acid ester compound as a vulcanizing agent is used at a ratio of about 0.1 to 10 parts by weight, preferably about 0.5 to 5 parts by weight, per 100 parts by weight of the carboxyl group-containing acrylic elastomer. If the proportion of this vulcanizing agent used is less than this, vulcanization becomes insufficient, and sufficient physical properties cannot be obtained in terms of tensile strength, compression set, and the like. On the other hand, if it is used in a larger proportion than this, the elongation at break will decrease and the compression set will worsen.
カルバミン酸エステル化合物加硫剤には、塩基性加硫促進剤を併用することもできる。塩基性加硫促進剤としては、グアニジン化合物あるいは1,8-ジアザビシクロ〔5.4.0〕ウンデセン-7、1,5-ジアザビシクロ〔4.3.0〕ノネン-5等のジアザビシクロアルケン化合物またはその有機酸塩、無機酸塩が用いられ、好ましくはその添加効果がより高いといった観点から、1,8-ジアザビシクロ〔5.4.0〕ウンデセン-7が用いられる。また、1,8-ジアザビシクロ〔5.4.0〕ウンデセン-7とシリカとの混合物を用いることもでき、実際にはSafic Alcan社製品Vulcofac ACT55等が用いられる。 A basic vulcanization accelerator can also be used in combination with the carbamic acid ester compound vulcanizing agent. Examples of the basic sulfide accelerator include guanidine compounds or diazabicycloalkene compounds such as 1,8-diazabicyclo [5.4.0] undecene-7 and 1,5-diazabicyclo [4.3.0] nonene-5, or organic acids thereof. Salts and inorganic acid salts are used, and 1,8-diazabicyclo [5.4.0] undecene-7 is used from the viewpoint that the addition effect thereof is preferably higher. A mixture of 1,8-diazabicyclo [5.4.0] undecene-7 and silica can also be used, and in practice, Safic Alcan's Vulcofac ACT55 and the like are used.
ジアザビシクロアルケン化合物の有機酸塩または無機酸塩を形成する化合物としては、塩酸、硫酸、カルボン酸、スルホン酸、フェノール等が挙げられる。カルボン酸としては、例えばオクチル酸、オレイン酸、ギ酸、オルソフタル酸、アジピン酸等が、またスルホン酸としては、ベンゼンスルホン酸、トルエンスルホン酸、ドデシルベンゼンスルホン酸、ナフタレンスルホン酸等が挙げられる。これらは単独または二種以上を併用することができる。 Examples of the compound forming an organic acid salt or an inorganic acid salt of the diazabicycloalkene compound include hydrochloric acid, sulfuric acid, carboxylic acid, sulfonic acid, phenol and the like. Examples of the carboxylic acid include octyl acid, oleic acid, formic acid, orthophthalic acid, adipic acid and the like, and examples of the sulfonic acid include benzenesulfonic acid, toluenesulfonic acid, dodecylbenzenesulfonic acid and naphthalenesulfonic acid. These can be used alone or in combination of two or more.
グアニジン化合物としては、グアニジンまたはその置換体、例えばアミノグアニジン、1,1,3,3-テトラメチルグアニジン、n-ドデシルグアニジン、メチロールグアニジン、ジメチロールグアニジン、1-フェニルグアニジン、1,3-ジフェニルグアニジン、1,3-ジ-o-トリルグアニジン、トリフェニルグアニジン、1-ベンジル-2,3-ジメチルグアニジン、シアノグアニジン等が用いられ、この他1,6-グアニジノヘキサン、グアニル尿素、ビグアニド、1-o-トリルビグアニド等も用いられる。 Examples of the guanidine compound include guanidine or a substitute thereof, for example, aminoguanidine, 1,1,3,3-tetramethylguanidine, n-dodecylguanidine, methylolguanidine, dimethylolguanidine, 1-phenylguanidine, 1,3-diphenylguanidine. , 1,3-di-o-tolylguanidine, triphenylguanidine, 1-benzyl-2,3-dimethylguanidine, cyanoguanidine, etc. are used, and 1,6-guanidinohexane, guanylurea, biguanide, 1- o-Trillubiguanide etc. are also used.
塩基性加硫促進剤としてのグアニジン化合物は、カルボキシル基含有アクリルゴム100重量部当り約0.1〜10重量部、好ましくは約0.3〜6重量部の割合で用いられ、前記ジアザビシクロアルケン化合物は約0.01〜2重量部、好ましくは約0.05〜1.0重量部の割合で用いられる。また、ジアザビシクロアルケン化合物の有機酸塩または無機酸塩は、カルボキシル基含有アクリルゴム100重量部当り約0.1〜5重量部、好ましくは約0.2〜2重量部の割合で用いられる。塩基性加硫促進剤の添加割合がこれより多い割合で用いられると、スコーチが短くなり好ましくない。 The guanidine compound as a basic sulfide accelerator is used in a proportion of about 0.1 to 10 parts by weight, preferably about 0.3 to 6 parts by weight per 100 parts by weight of the carboxyl group-containing acrylic rubber, and the diazabicycloalkene compound is about. It is used in a proportion of 0.01 to 2 parts by weight, preferably about 0.05 to 1.0 parts by weight. The organic acid salt or inorganic acid salt of the diazabicycloalkene compound is used in a proportion of about 0.1 to 5 parts by weight, preferably about 0.2 to 2 parts by weight, per 100 parts by weight of the carboxyl group-containing acrylic rubber. If the addition ratio of the basic vulcanization accelerator is higher than this, the scorch becomes short, which is not preferable.
アクリルゴム組成物の調製は、カルボキシル基含有アクリルゴムおよびゴムの配合剤等として一般に用いられているカーボンブラック、シリカ等の無機充填剤、滑剤、老化防止剤、その他必要な配合剤をバンバリーミキサ等の密閉型混練機で混練した後、加硫剤および加硫促進剤を加え、オープンロールを用いて混合することにより行われる。調製されたアクリルゴム組成物は、一般に約150〜200℃、約1〜60分間のプレス加硫(一次加硫)によって加硫され、必要に応じて約150〜200℃、約1〜10時間のオーブン加硫(二次加硫)が行われる。 Acrylic rubber compositions are prepared by using inorganic fillers such as carbon black and silica, which are generally used as compounding agents for carboxyl group-containing acrylic rubber and rubber, lubricants, antiaging agents, and other necessary compounding agents such as Banbury mixer. After kneading with the closed type kneader, a vulcanizing agent and a vulcanization accelerator are added, and the mixture is mixed using an open roll. The prepared acrylic rubber composition is generally vulcanized by press vulcanization (primary vulcanization) at about 150 to 200 ° C. for about 1 to 60 minutes, and if necessary, about 150 to 200 ° C. for about 1 to 10 hours. Oven vulcanization (secondary vulcanization) is performed.
次に、実施例について本発明を説明する。 Next, the present invention will be described with respect to Examples.
実施例１
容量200mlのナスフラスコに、インドリルメタノール(東京化成工業製品)11.00g(74.7ミリモル)およびメチルエチルケトン24gを仕込み、25℃の水浴中で攪拌させることにより溶解させた後、ジラウリン酸ジブチルスズ(富士フイルム和光純薬製品)144mg(0.228ミリモル)を溶解させたメチルエチルケトン溶液2gを加え、続いてヘキサメチレンジイソシアネート(東京化成工業製品)6.00g(35.6ミリモル)のメチルエチルケトン溶液24gを2〜3回に分けて滴下し、5分間放置した。
Example 1
11.00 g (74.7 mmol) of indrill methanol (Tokyo Kasei Kogyo product) and 24 g of methyl ethyl ketone were placed in a 200 ml eggplant flask and dissolved by stirring in a water bath at 25 ° C. Then dibutyltin dilaurate (Fujifilm sum). 2 g of a methyl ethyl ketone solution in which 144 mg (0.228 mmol) of photopure drug product was dissolved was added, and then 24 g of a methyl ethyl ketone solution of 6.00 g (35.6 mmol) of hexamethylene diisocyanate (Tokyo Kasei Kogyo product) was added dropwise in 2 to 3 portions. , Left for 5 minutes.
反応終了後、減圧下において室温下にて5時間乾燥し、薄褐色の粗製粉末状固体〔カルバミン酸エステル化合物Ａ〕17.24gを得た。
得られた固体は、1H NMR(Aceton-d6)およびFT-IRを用いてその構造を同定した。
(b) 7.1ppm (t 2H)
(c),(d) 7.4ppm (m 4H)
(e) 10.2ppm (s 2H)
(f) 7.0ppm (t 2H)
(g) 5.3ppm (s 4H)
(h) 6.1ppm (s 2H)
(i) 3.1ppm (q 4H)
(j) 1.5ppm (m 4H)
(k) 1.3ppm (m 4H)
FT-IR：3385cm-1：第2級複素芳香族アミンのN-H伸縮振動
3324cm-1：ウレタン結合由来のN-H伸縮振動
1686cm-1：ウレタン結合由来のC=O伸縮振動
The structure of the obtained solid was identified using 1 H NMR (Aceton-d 6 ) and FT-IR.
(b) 7.1ppm (t 2H)
(c), (d) 7.4ppm (m 4H)
(e) 10.2ppm (s 2H)
(f) 7.0ppm (t 2H)
(g) 5.3ppm (s 4H)
(h) 6.1ppm (s 2H)
(i) 3.1ppm (q 4H)
(j) 1.5ppm (m 4H)
(k) 1.3ppm (m 4H)
FT-IR: 3385cm -1 : NH expansion and contraction vibration of secondary complex aromatic amine
3324cm -1 : NH expansion and contraction vibration derived from urethane bond
1686cm -1 : C = O expansion and contraction vibration derived from urethane bond
実施例２
容量50mlのナスフラスコに、N-メチル-2-ヒドロキシメチルピロール(東京化成工業製品)6.23g(56.1ミリモル)を仕込み、ジラウリン酸ジブチルスズ 108mg(0.171ミリモル)を溶解させたメチルエチルケトン溶液2gを加え、続いてヘキサメチレンジイソシアネート 4.50g(26.7ミリモル)を溶解させたメチルエチルケトン溶液6gを滴下し、25℃の水浴中で1.5時間攪拌した。
Example 2
To a 50 ml eggplant flask, 6.23 g (56.1 mmol) of N-methyl-2-hydroxymethylpyrrole (Tokyo Kasei Kogyo product) was charged, and 2 g of a methylethylketone solution in which 108 mg (0.171 mmol) of dibutyltin dilaurate was dissolved was added, followed by 6 g of a methyl ethyl ketone solution in which 4.50 g (26.7 mmol) of hexamethylene diisocyanate was dissolved was added dropwise, and the mixture was stirred in a water bath at 25 ° C. for 1.5 hours.
反応終了後、減圧下において室温にて8時間乾燥し、薄褐色の粉末状固体〔カルバミン酸エステル化合物Ｂ〕10.79g(収率99％)を得た。
得られた固体は、1H NMRおよびFT-IRを用いてその構造を同定した。
(b) 6.6ppm (t 2H)
(c) 6.2ppm (q 2H)
(d) 6.1ppm (t 2H)
(e) 5.0ppm (s 4H)
(f) 6.6ppm (s 2H)
(g) 3.1ppm (m 4H)
(h) 1.5ppm (m 4H)
(i) 1.3ppm (m 4H)
FT-IR：3325cm-1：ウレタン結合由来のN-H伸縮振動
1679cm-1：ウレタン結合由来のC=O伸縮振動
The structure of the obtained solid was identified using 1 H NMR and FT-IR.
(b) 6.6ppm (t 2H)
(c) 6.2ppm (q 2H)
(d) 6.1ppm (t 2H)
(e) 5.0ppm (s 4H)
(f) 6.6ppm (s 2H)
(g) 3.1ppm (m 4H)
(h) 1.5ppm (m 4H)
(i) 1.3ppm (m 4H)
FT-IR: 3325cm -1 : NH expansion and contraction vibration derived from urethane bond
1679cm -1 : C = O expansion and contraction vibration derived from urethane bond
実施例３
容量100mlの二口ナスフラスコに、1,1-ジフェニルエタノール(東京化成工業製品)11.16g(56.25ミリモル)を仕込み、ジラウリン酸ジブチルスズ 360mg(0.570ミリモル)を溶解させたメチルエチルケトン溶液2gを加えた後、ヘキサメチレンジイソシアネート4.50g(26.7ミリモル)を溶解させたメチルエチルケトン溶液4gを滴下し、反応器を80℃に加温して5.5時間攪拌した。
Example 3
11.16 g (56.25 mmol) of 1,1-diphenylethanol (Tokyo Kasei Kogyo product) was charged into a two-necked eggplant flask with a capacity of 100 ml, and 2 g of a methylethylketone solution in which 360 mg (0.570 mmol) of dibutyltin dilaurate was dissolved was added. 4 g of a methyl ethyl ketone solution in which 4.50 g (26.7 mmol) of hexamethylene diisocyanate was dissolved was added dropwise, and the reactor was heated to 80 ° C. and stirred for 5.5 hours.
反応終了後、不溶部をろ過してn-ヘキサンで洗い、ろ過物を減圧下において室温にて8時間乾燥し、白色の粉末状固体〔カルバミン酸エステル化合物Ｃ〕14.25g(収率94％)を得た。
得られた固体は、1H NMRおよびFT-IRを用いてその構造を同定した。
(d) 2.2ppm (s 6H)
(c),(d) 7.4ppm (m 4H)
(e) 4.8ppm (s 2H)
(f) 3.0ppm (m 4H)
(g) 1.4ppm (m 4H)
(h) 1.2ppm (m 4H)
FT-IR：3281cm-1：ウレタン結合由来のN-H伸縮振動
1690cm-1：ウレタン結合由来のC=O伸縮振動
The structure of the obtained solid was identified using 1 H NMR and FT-IR.
(d) 2.2ppm (s 6H)
(c), (d) 7.4ppm (m 4H)
(e) 4.8ppm (s 2H)
(f) 3.0ppm (m 4H)
(g) 1.4ppm (m 4H)
(h) 1.2ppm (m 4H)
FT-IR: 3281cm -1 : NH expansion and contraction vibration derived from urethane bond
1690cm -1 : C = O expansion and contraction vibration derived from urethane bond
参考例
容量50mlのナスフラスコに、α,α,4-トリメチル-ジメチルベンジルアルコール(東京化成工業製品)8.43g(56.1ミリモル)、ジラウリン酸ジブチルスズ 360mg(0.570ミリモル)およびヘキサメチレンジイソシアネート 4.50g(26.7ミリモル)を仕込み、反応器を80℃に加温し、2.5時間攪拌した。
Reference example In a 50 ml capacity eggplant flask, 8.43 g (56.1 mmol) of α, α, 4-trimethyl-dimethylbenzyl alcohol (Tokyo Chemical Industry product), 360 mg (0.570 mmol) of dibutyltin dilaurate and 4.50 g (26.7 mmol) of hexamethylene diisocyanate. ) Was charged, the reactor was heated to 80 ° C., and the mixture was stirred for 2.5 hours.
反応終了後冷却し、白色の粉末状固体〔カルバミン酸エステル化合物Ｄ〕12.06g(収率91％)を得た。
得られた固体は、1H NMRおよびFT-IRを用いてその構造を同定した。
(b) 7.1ppm (t 2H)
(c) 7.2ppm (m 4H)
(d) 1.7ppm (s 12H)
(e) 4.7ppm (m 2H)
(f) 3.0ppm (m 4H)
(g) 1.4ppm (m 4H)
(h) 1.3ppm (m 4H)
FT-IR：3307cm-1：ウレタン結合由来のN-H伸縮振動
1687cm-1：ウレタン結合由来のC=O伸縮振動
The structure of the obtained solid was identified using 1 H NMR and FT-IR.
(b) 7.1ppm (t 2H)
(c) 7.2ppm (m 4H)
(d) 1.7ppm (s 12H)
(e) 4.7ppm (m 2H)
(f) 3.0ppm (m 4H)
(g) 1.4ppm (m 4H)
(h) 1.3ppm (m 4H)
FT-IR: 3307cm -1 : NH expansion and contraction vibration derived from urethane bond
1687cm -1 : C = O expansion and contraction vibration derived from urethane bond
実施例４
カルボキシル基含有アクリルゴム 100重量部
(ユニマテック製品ノックスタイトPA-522HF)
FEFカーボンブラック(東海カーボン製品シーストG-SO) 55 〃
ステアリン酸(ミヨシ油脂製品DTST) 1 〃
4,4′-(α,α-ジメチルベンジル)ジフェニルアミン 2 〃
(大内新興化学工業製品ノクラックCD)
カルバミン酸エステル化合物Ａ 1.7 〃
1,3-ジ-o-トリルグアニジン 2 〃
(大内新興化学工業製品ノクセラーDT)
Example 4
Carboxylic group-containing acrylic rubber 100 parts by weight
(Unimatec product Knox tight PA-522HF)
FEF Carbon Black (Tokai Carbon Product Seest G-SO) 55 〃
Stearic acid (Miyoshi Oil & Fat Product DTST) 1 〃
4,4'-(α, α-dimethylbenzyl) diphenylamine 2 〃
(Ouchi Shinko Chemical Industry Product Nocrack CD)
Carbamic acid ester compound A 1.7 〃
1,3-di-o-trill guanidine 2 〃
(Ouchi Shinko Chemical Industry Product Noxeller DT)
以上の各成分の内、加硫剤および加硫促進剤を除く各成分をバンバリーミキサで混練した後、オープンロールを用いて加硫剤および加硫促進剤の添加が行われた。このようにして調製されたアクリルゴム組成物は、180℃で8分間のプレス加硫(一次加硫)および175℃、4時間のオーブン加硫(二次加硫)によって加硫された。 Of the above components, each component excluding the vulcanizing agent and the vulcanization accelerator was kneaded with a Banbury mixer, and then the vulcanizing agent and the vulcanization accelerator were added using an open roll. The acrylic rubber composition thus prepared was vulcanized by press vulcanization (primary vulcanization) at 180 ° C. for 8 minutes and oven vulcanization (secondary vulcanization) at 175 ° C. for 4 hours.
アクリルゴム組成物である生地の加硫特性および加硫物物性の測定が、次のようにして行われた。
ムーニー・スコーチ試験：ISO 289に対応するJIS K6300-1準拠
(125℃)
t5の値(単位：分)は長い程成形時の生地ヤ
ケの懸念が少なく、ヤケに起因する不良が
少ない
一般には、t5の値が10分以上であれば、射
出成形、圧縮成形、押出成形でのヤケに起
因する不良が少なくなる
MLmin：ムーニー粘度の最低値であり、加工
性の指標となる
加硫試験：ISO 6502に対応するJIS K6300-2準拠(180℃、12分間)
東洋精機製作所製ロータレス・レオメーターRLR-3使用
ML：最小トルク
MH：最大トルク
tc10：加硫トルクがML+(MH-ML)×0.1に達するまでに要す
る時間
tc90：加硫トルクがML+(MH-ML)×0.9に達するまでに要す
る時間
加硫速度の評価は、加硫試験のtc10、tc90およびME(MH-
ML)で判断でき、tc10およびtc90が短くかつMEが大きい程
加硫速度は速い
常態値：ISO 37に対応するJIS K6251、ISO 7619-1に対応するJIS K62
53準拠
圧縮永久歪：ISO 815-1に対応するJIS K6262準拠(175℃、70時間)
空気加熱老化試験：ISO 188に対応するJIS K6257準拠(175℃、70時
間)常態値変化を測定
The vulcanization properties and physical properties of the vulcanized material of the dough, which is an acrylic rubber composition, were measured as follows.
Mooney Scorch Test: JIS K 6300-1 compliant for ISO 289
(125 ℃)
The longer the value of t5 (unit: minutes), the more the dough at the time of molding.
There is little concern about burns, and defects caused by burns
Few
In general, if the value of t5 is 10 minutes or more, it will fire
Caused by discoloration in ejection molding, compression molding, and extrusion molding
Fewer defects caused
ML min : The lowest value of Mooney viscosity, processed
Vulcanization test as an index of sex: JIS K 6300-2 compliant (180 ° C, 12 minutes) corresponding to ISO 6502
Uses Toyo Seiki Seisakusho's rotary rheometer RLR-3
ML: Minimum torque
MH: Maximum torque
tc10: It takes time for the vulcanization torque to reach ML + (MH-ML) x 0.1.
Time
tc90: It takes time for the vulcanization torque to reach ML + (MH-ML) x 0.9.
Time
Evaluation of vulcanization rate is based on vulcanization tests tc10, tc90 and ME (MH-
Judgment by ML), the shorter tc10 and tc90 and the larger ME
Vulcanization rate is fast Normal value: JIS K6251 corresponding to ISO 37, JIS K62 corresponding to ISO 7619-1
53 compliant compression set: JIS K 6262 compliant (175 ° C, 70 hours) corresponding to ISO 815-1
Air heating aging test: JIS K 6257 compliant (175 ° C, 70 o'clock) corresponding to ISO 188
Between) Measure changes in normal values
実施例５
実施例４において、カルバミン酸エステル化合物Ａの代わりに、カルバミン酸エステル化合物Ｂ1.5重量部が用いられた。
Example 5
In Example 4 , 1.5 parts by weight of the carbamic acid ester compound B was used instead of the carbamic acid ester compound A.
実施例６
実施例４において、カルバミン酸エステル化合物Ａの代わりに、カルバミン酸エステル化合物Ｃ2.1重量部が用いられた。
Example 6
In Example 4 , 2.1 parts by weight of the carbamic acid ester compound C was used instead of the carbamic acid ester compound A.
実施例７
実施例４において、カルバミン酸エステル化合物Ａの代わりに、カルバミン酸エステル化合物Ｄ1.8重量部が用いられた。
Example 7
In Example 4 , 1.8 parts by weight of the carbamic acid ester compound D was used instead of the carbamic acid ester compound A.
比較例１
実施例４において、カルバミン酸エステル化合物Ａの代わりに、脂肪族アミン加硫剤(ユニマテック製品ケミノックスAC-6F)0.6重量部が用いられた。
Comparative Example 1
In Example 4 , 0.6 parts by weight of an aliphatic amine vulcanizer (Unimatec product Cheminox AC-6F) was used instead of the carbamic acid ester compound A.
比較例２
実施例４において、カルバミン酸エステル化合物Ａの代わりに、芳香族ジアミン加硫剤(ユニマテック製品ケミノックスCLP5000)1.2重量部が用いられた。
Comparative Example 2
In Example 4 , 1.2 parts by weight of an aromatic diamine vulcanizer (Unimatec product Cheminox CLP5000) was used instead of the carbamic acid ester compound A.
比較例３
比較例１において、さらに加硫遅延剤としてステアリルアミン(花王製品ファーミン80S)1重量部が用いられた。
Comparative Example 3
In Comparative Example 1, 1 part by weight of stearylamine (Kao product Fermin 80S) was further used as a vulcanization retarder.
実施例８
実施例６において、1,3-ジ-o-トリルグアニジンの代わりに、加硫促進剤として1,8-ジアザビシクロ〔5.4.0〕ウンデセン-7二塩基酸塩−アルファモスシリカ(重量比70：30)混合物(Safic Alcan社製品Vulcofac ACT55) 1重量部が用いられた。
Example 8
In Example 6 , instead of 1,3-di-o-tolylguanidine, 1,8-diazabicyclo [5.4.0] undecene-7 dibasate-alphamos silica (weight ratio 70:) as a vulcanization accelerator. 30) Mixture (Vulcofac ACT55, manufactured by Safic Alcan) 1 part by weight was used.
実施例９
実施例７において、1,3-ジ-o-トリルグアニジンの代わりに、加硫促進剤として1,8-ジアザビシクロ〔5.4.0〕ウンデセン-7二塩基酸塩−アルファモスシリカ(重量比70：30)混合物(Vulcofac ACT55) 1重量部が用いられた。
Example 9
In Example 7 , instead of 1,3-di-o-tolylguanidine, 1,8-diazabicyclo [5.4.0] undecene-7 dibasate-alphamos silica (weight ratio 70:) as a vulcanization accelerator. 30) 1 part by weight of the mixture (Vulcofac ACT55) was used.
比較例４
比較例１において、1,3-ジ-o-トリルグアニジンの代わりに、加硫促進剤として1,8-ジアザビシクロ〔5.4.0〕ウンデセン-7二塩基酸塩−アルファモスシリカ(重量比70：30)混合物(Vulcofac ACT55) 1重量部が用いられた。
Comparative Example 4
In Comparative Example 1, instead of 1,3-di-o-tolylguanidine, 1,8-diazabicyclo [5.4.0] undecene-7 dibasic acid salt-alpha moss silica (weight ratio 70:) was used as a vulcanization accelerator. 30) 1 part by weight of the mixture (Vulcofac ACT55) was used.
比較例５
比較例３において、1,3-ジ-o-トリルグアニジンの代わりに、加硫促進剤として1,8-ジアザビシクロ〔5.4.0〕ウンデセン-7二塩基酸塩−アルファモスシリカ(重量比70：30)混合物(Vulcofac ACT55) 1重量部が用いられた。
Comparative Example 5
In Comparative Example 3, instead of 1,3-di-o-tolylguanidine, 1,8-diazabicyclo [5.4.0] undecene-7 dibasate-alphamos silica (weight ratio 70:) was used as a vulcanization accelerator. 30) 1 part by weight of the mixture (Vulcofac ACT55) was used.
以上の実施例４〜９および比較例１〜５で得られた結果は、次の表１に示される。
表１
実施例 比較例 実施例 比較例
測定項目 ４ ５ ６ ７ １ ２ ３ ８ ９ ４ ５
ムーニー・スコーチ試験
MLmin (pts) 33 32 29 29 32 32 32 29 28 36 36
t5 (分) 7.9 8.0 18.6 26.3 6.8 13.5 8.1 17.4 18.3 5.4 6.2
加硫試験
tc10 (分) 0.60 0.62 0.89 1.12 0.58 1.19 0.69 0.99 1.05 0.51 0.59
tc90 (分) 4.69 6.34 6.09 6.58 4.26 8.25 6.54 6.94 7.14 5.08 6.46
ML (N・m) 0.14 0.13 0.12 0.12 0.13 0.13 0.13 0.13 0.12 0.14 0.14
MH (N・m) 0.71 0.69 0.76 0.71 0.78 0.35 0.64 0.78 0.75 0.82 0.67
ME(MH - ML) (N・m) 0.57 0.56 0.64 0.59 0.65 0.22 0.51 0.65 0.63 0.68 0.53
常態値
硬度 (デュロA) 63 66 65 61 61 67 63 66 65 61 64
100％モジュラス(MPa) 4.1 5.0 4.9 4.1 3.7 4.8 3.5 5.2 4.7 4.3 4.0
破断強度 (MPa) 11.2 12.0 10.8 10.5 11.4 11.9 10.8 11.5 11.4 11.9 11.3
破断時伸び (％) 250 210 220 250 240 220 270 200 210 210 230
圧縮永久歪
175℃、70時間 (％) 14 18 16 16 12 15 23 19 16 13 20
175℃、70時間後の常態値変化
硬度 (デュロA) +2 +2 +2 +4 +2 +2 -3 +1 +1 +3 +2
100％モジュラス(MPa) -23 -20 -15 -11 -12 -5 -16 -14 -21 -18 -20
破断強度 (MPa) -18 -12 -9 -10 -16 -9 -18 -15 -17 -19 -18
破断時伸び (％) +20 +14 +18 +4 +13 0 +7 +20 +14 +19 +17
The results obtained in Examples 4 to 9 and Comparative Examples 1 to 5 above are shown in Table 1 below.
Table 1
Example Comparative Example Example Comparative Example
Measurement items 4 5 6 7 1 2 3 8 9 4 5
Mooney Scorch Exam
ML min (pts) 33 32 29 29 32 32 32 29 28 36 36
t5 (minutes) 7.9 8.0 18.6 26.3 6.8 13.5 8.1 17.4 18.3 5.4 6.2
Vulcanization test
tc10 (minutes) 0.60 0.62 0.89 1.12 0.58 1.19 0.69 0.99 1.05 0.51 0.59
tc90 (minutes) 4.69 6.34 6.09 6.58 4.26 8.25 6.54 6.94 7.14 5.08 6.46
ML (N ・ m) 0.14 0.13 0.12 0.12 0.13 0.13 0.13 0.13 0.12 0.14 0.14
MH (N ・ m) 0.71 0.69 0.76 0.71 0.78 0.35 0.64 0.78 0.75 0.82 0.67
ME (MH --ML) (N ・ m) 0.57 0.56 0.64 0.59 0.65 0.22 0.51 0.65 0.63 0.68 0.53
Normal value Hardness (Duro A) 63 66 65 61 61 67 63 66 65 61 64
100% Modulus (MPa) 4.1 5.0 4.9 4.1 3.7 4.8 3.5 5.2 4.7 4.3 4.0
Breaking strength (MPa) 11.2 12.0 10.8 10.5 11.4 11.9 10.8 11.5 11.4 11.9 11.3
Elongation at break (%) 250 210 220 250 240 220 270 200 210 210 230
Compression permanent strain
175 ℃, 70 hours (%) 14 18 16 16 12 15 23 19 16 13 20
Normal value change after 70 hours at 175 ℃ Hardness (Duro A) +2 +2 +2 +4 +2 +2 -3 +1 +1 +3 +2
100% Modulus (MPa) -23 -20 -15 -11 -12 -5 -16 -14 -21 -18 -20
Breaking strength (MPa) -18 -12 -9 -10 -16 -9 -18 -15 -17 -19 -18
Elongation at break (%) +20 +14 +18 +4 +13 0 +7 +20 +14 +19 +17
実施例１０
実施例５において、1,3-ジ-o-トリルグアニジンの代わりに、加硫促進剤として1,8-ジアザビシクロ〔5.4.0〕ウンデセン-7(ランクセス社製品Rhenogran XLA-60) 1重量部が用いられた。
Example 10
In Example 5 , instead of 1,3-di-o-tolylguanidine, 1 part by weight of 1,8-diazabicyclo [5.4.0] undecene-7 (Lanxess product Rhenogran XLA-60) was used as a vulcanization accelerator. Was used.
実施例１１
実施例６において、1,3-ジ-o-トリルグアニジンの代わりに、加硫促進剤として1,8-ジアザビシクロ〔5.4.0〕ウンデセン-7(Rhenogran XLA-60) 1重量部が用いられた。
Example 11
In Example 6 , 1 part by weight of 1,8-diazabicyclo [5.4.0] undecene-7 (Rhenogran XLA-60) was used as a vulcanization accelerator instead of 1,3-di-o-tolylguanidine. ..
実施例１２
実施例７において、1,3-ジ-o-トリルグアニジンの代わりに、加硫促進剤として1,8-ジアザビシクロ〔5.4.0〕ウンデセン-7(Rhenogran XLA-60) 1重量部が用いられた。
Example 12
In Example 7 , 1 part by weight of 1,8-diazabicyclo [5.4.0] undecene-7 (Rhenogran XLA-60) was used as a vulcanization accelerator instead of 1,3-di-o-tolylguanidine. ..
比較例６
比較例１において、1,3-ジ-o-トリルグアニジンの代わりに、加硫促進剤として1,8-ジアザビシクロ〔5.4.0〕ウンデセン-7(Rhenogran XLA-60) 1重量部が用いられた。
Comparative Example 6
In Comparative Example 1, 1 part by weight of 1,8-diazabicyclo [5.4.0] undecene-7 (Rhenogran XLA-60) was used as a vulcanization accelerator instead of 1,3-di-o-tolylguanidine. ..
比較例７
比較例３において、1,3-ジ-o-トリルグアニジンの代わりに、加硫促進剤として1,8-ジアザビシクロ〔5.4.0〕ウンデセン-7(Rhenogran XLA-60) 1重量部が用いられた。
Comparative Example 7
In Comparative Example 3, 1 part by weight of 1,8-diazabicyclo [5.4.0] undecene-7 (Rhenogran XLA-60) was used as a vulcanization accelerator instead of 1,3-di-o-tolylguanidine. ..
実施例１３
実施例６において、1,3-ジ-o-トリルグアニジンの代わりに、加硫促進剤として1,8-ジアザビシクロ〔5.4.0〕ウンデセン-7(サンアプロ製品DBU) 0.5重量部が用いられた。
Example 13
In Example 6 , 0.5 part by weight of 1,8-diazabicyclo [5.4.0] undecene-7 (San Apro product DBU) was used as a vulcanization accelerator instead of 1,3-di-o-tolylguanidine.
実施例１４
実施例７において、1,3-ジ-o-トリルグアニジンの代わりに、加硫促進剤として1,8-ジアザビシクロ〔5.4.0〕ウンデセン-7(DBU) 0.5重量部が用いられた。
Example 14
In Example 7 , 0.5 parts by weight of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) was used as the vulcanization accelerator instead of 1,3-di-o-tolylguanidine.
比較例８
比較例１において、1,3-ジ-o-トリルグアニジンの代わりに、加硫促進剤として1,8-ジアザビシクロ〔5.4.0〕ウンデセン-7(DBU) 0.5重量部が用いられた。
Comparative Example 8
In Comparative Example 1, 0.5 part by weight of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) was used as a vulcanization accelerator instead of 1,3-di-o-tolylguanidine.
比較例９
比較例３において、1,3-ジ-o-トリルグアニジンの代わりに、加硫促進剤として1,8-ジアザビシクロ〔5.4.0〕ウンデセン-7(DBU) 0.5重量部が用いられた。
Comparative Example 9
In Comparative Example 3, 0.5 part by weight of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) was used as a vulcanization accelerator instead of 1,3-di-o-tolylguanidine.
比較例１０
実施例１において、FEFカーボンブラック量が60重量部に変更され、カルバミン酸エステル化合物Aの代りに、1.5重量部のHMDA-Fmocが用いられた。
In Example 1, the amount of FEF carbon black was changed to 60 parts by weight and 1.5 parts by weight of HMDA-Fmoc was used instead of carbamic acid ester compound A.
比較例１１
実施例１において、FEFカーボンブラック量が60重量部に変更され、カルバミン酸エステル化合物Aの代りに、1.5重量部のHMDA-Dmocが用いられた。
In Example 1, the amount of FEF carbon black was changed to 60 parts by weight and 1.5 parts by weight of HMDA-Dmoc was used instead of carbamic acid ester compound A.
以上の実施例１０〜１４および比較例６〜１１で得られた結果は、次の表２に示される。
表２
実施例 比較例 実施例 比較例
測定項目 10 11 12 ６ ７ 13 14 ８ ９ 10 11
ムーニー・スコーチ試験
MLmin (pts) 34 30 30 38 36 35 34 41 37 36 36
t5 (分) 9.3 24.6 25.2 6.0 7.8 18.0 23.3 4.0 5.2 >60 >60
加硫試験
tc10 (分) 0.83 1.24 1.30 0.65 0.70 1.08 1.20 0.36 0.47 2.74 1.65
tc90 (分) 7.39 7.39 7.52 6.31 7.25 6.33 6.62 3.53 4.79 9.20 8.92
ML (N・m) 0.13 0.12 0.12 0.14 0.14 0.13 0.13 0.15 0.14 0.16 0.15
MH (N・m) 0.70 0.70 0.67 0.77 0.63 0.82 0.81 0.88 0.69 0.41 0.32
ME(MH - ML) (N・m) 0.57 0.58 0.55 0.63 0.49 0.69 0.68 0.73 0.55 0.25 0.17
常態値
硬度 (デュロA) 66 65 64 61 62 69 66 65 66 65 62
100％モジュラス(MPa) 4.9 4.5 4.2 4.5 3.9 5.9 5.1 5.7 4.3 2.5 2.8
破断強度 (MPa) 10.8 11.0 10.3 11.7 11.3 11.7 11.4 12.3 11.6 9.2 8.9
破断時伸び (％) 200 230 220 220 230 190 200 180 220 310 340
圧縮永久歪
175℃、70時間 (％) 23 24 20 16 22 23 19 15 21 15 26
175℃、70時間後の常態値変化
硬度 (デュロA) +4 +0 +3 +4 +3 +4 +4 +0 +1 − −
100％モジュラス(MPa) -15 -21 -2 -20 -13 -29 -16 -30 -19 − −
破断強度 (MPa) -9 -18 -5 -19 -18 -17 -14 -17 -17 − −
破断時伸び (％) +15 +13 +18 +18 +17 +21 +10 +28 +9 − −
The results obtained in Examples 10 to 14 and Comparative Examples 6 to 11 above are shown in Table 2 below.
Table 2
Example Comparative Example Example Comparative Example
Measurement items 10 11 12 6 7 13 14 8 9 10 11
Mooney Scorch Exam
ML min (pts) 34 30 30 38 36 35 34 41 37 36 36
t5 (minutes) 9.3 24.6 25.2 6.0 7.8 18.0 23.3 4.0 5.2>60> 60
Vulcanization test
tc10 (minutes) 0.83 1.24 1.30 0.65 0.70 1.08 1.20 0.36 0.47 2.74 1.65
tc90 (minutes) 7.39 7.39 7.52 6.31 7.25 6.33 6.62 3.53 4.79 9.20 8.92
ML (N ・ m) 0.13 0.12 0.12 0.14 0.14 0.13 0.13 0.15 0.14 0.16 0.15
MH (N ・ m) 0.70 0.70 0.67 0.77 0.63 0.82 0.81 0.88 0.69 0.41 0.32
ME (MH --ML) (N ・ m) 0.57 0.58 0.55 0.63 0.49 0.69 0.68 0.73 0.55 0.25 0.17
Normal value Hardness (Duro A) 66 65 64 61 62 69 66 65 66 65 62
100% Modulus (MPa) 4.9 4.5 4.2 4.5 3.9 5.9 5.1 5.7 4.3 2.5 2.8
Breaking strength (MPa) 10.8 11.0 10.3 11.7 11.3 11.7 11.4 12.3 11.6 9.2 8.9
Elongation at break (%) 200 230 220 220 230 190 200 180 220 310 340
Compression permanent strain
175 ℃, 70 hours (%) 23 24 20 16 22 23 19 15 21 15 26
Normal value change after 70 hours at 175 ℃ Hardness (Duro A) +4 +0 +3 +4 +3 +4 +4 +0 +1 − −
100% Modulus (MPa) -15 -21 -2 -20 -13 -29 -16 -30 -19 − −
Breaking strength (MPa) -9 -18 -5 -19 -18 -17 -14 -17 -17 − −
Elongation at break (%) +15 +13 +18 +18 +17 +21 +10 +28 +9 − −
Claims (9)
Z-OCONH(CH2)nNHCOO-Z 〔Ｉ〕
ここでZは下記〔i〕、〔ii〕または〔iii〕であり、nは2〜10の整数である
Z-OCONH (CH 2 ) n NHCOO-Z [I]
Where Z is the following [i], [ii] or [iii], and n is an integer from 2 to 10.
Z-OCONH(CH2)nNHCOO-Z 〔Ｉ〕
ここでZは下記〔i〕、〔ii〕または〔iii〕であり、nは2〜10の整数である
Z-OCONH (CH 2 ) n NHCOO-Z [I]
Where Z is the following [i], [ii] or [iii], and n is an integer from 2 to 10.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018217626 | 2018-11-20 | ||
| JP2018217626 | 2018-11-20 | ||
| PCT/JP2019/044669 WO2020105536A1 (en) | 2018-11-20 | 2019-11-14 | Novel carbamate ester compound and acrylic rubber composition containing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP6781863B1 true JP6781863B1 (en) | 2020-11-04 |
| JPWO2020105536A1 JPWO2020105536A1 (en) | 2021-02-15 |
Family
ID=70773311
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2020535273A Active JP6781863B1 (en) | 2018-11-20 | 2019-11-14 | New carbamic acid ester compound and acrylic rubber composition containing it |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US11932644B2 (en) |
| EP (1) | EP3885338A4 (en) |
| JP (1) | JP6781863B1 (en) |
| CN (1) | CN112955429B (en) |
| WO (1) | WO2020105536A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022059290A1 (en) * | 2020-09-15 | 2022-03-24 | ユニマテック株式会社 | Rubber composition |
Family Cites Families (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1418169A (en) * | 1972-02-25 | 1975-12-17 | Hitachi Chemical Co Ltd | Resist image formation process and resin compositions and materials for use in said process |
| US3962302A (en) * | 1974-03-08 | 1976-06-08 | Atlantic Richfield Company | Production of isocyanates from esters of carbamic acids (urethanes) |
| SU734231A1 (en) * | 1977-12-16 | 1980-05-15 | Предприятие П/Я В-8339 | Unsaturated rubber-based vulcanized rubber mixture |
| SU791742A1 (en) * | 1979-03-19 | 1980-12-30 | Волгоградский Политехнический Институт | 1-tert-butylperoxymethyl-6-tert-butylperoxyhexamethylenedicarbamate as structuration initiator possessing anhesive properties |
| IT1190368B (en) * | 1985-06-19 | 1988-02-16 | Monteflous Spa | COVULCANISABLE COMPOSITIONS OF FLUOROELASTOMERS |
| DE3819942A1 (en) * | 1988-06-11 | 1989-12-21 | Bayer Ag | METHOD FOR THE PRODUCTION OF CURTAINABLE BINDER COMBINATIONS, THE COMBINATIONS AVAILABLE BY THIS METHOD AND THEIR USE |
| JPH07145164A (en) | 1993-09-30 | 1995-06-06 | Nippon Zeon Co Ltd | Dithiocarbonate derivative and crosslinking method using the derivative |
| JP3837900B2 (en) | 1998-03-13 | 2006-10-25 | ユニマテック株式会社 | Acrylic elastomer composition |
| US6015860A (en) | 1997-09-26 | 2000-01-18 | Nippon Mektron, Limited | Acrylic elastomer composition |
| JPH11100478A (en) | 1997-09-26 | 1999-04-13 | Nippon Mektron Ltd | Acrylic elastomer composition |
| JP3663859B2 (en) | 1997-10-31 | 2005-06-22 | ユニマテック株式会社 | Acrylic elastomer composition |
| JP4345170B2 (en) | 1999-12-24 | 2009-10-14 | ユニマテック株式会社 | Heat-resistant air-based hose vulcanization molding composition |
| JP2001316554A (en) | 2000-02-29 | 2001-11-16 | Nippon Zeon Co Ltd | Acrylic rubber composition and crosslinked product |
| JP4634637B2 (en) | 2001-04-20 | 2011-02-16 | 電気化学工業株式会社 | Acrylic elastomer composition |
| JP3937172B2 (en) | 2001-07-05 | 2007-06-27 | 日本ゼオン株式会社 | Acrylic rubber composition containing acrylic rubber having carboxyl group in molecule, vulcanizing agent and vulcanization accelerator and use thereof |
| JP4022736B2 (en) | 2002-05-27 | 2007-12-19 | 日本ゼオン株式会社 | Acrylic rubber composition and cross-linked product |
| DE10237950A1 (en) * | 2002-08-20 | 2004-03-11 | Tesa Ag | Polyacrylate contact adhesive useful for making adhesive tape comprises a base-reactive polyacrylate thermally crosslinked with a photochemically generated base |
| JP4024219B2 (en) | 2003-02-21 | 2007-12-19 | 電気化学工業株式会社 | Carboxyl group-containing acrylic rubber composition |
| JP4729887B2 (en) | 2004-04-21 | 2011-07-20 | ユニマテック株式会社 | Acrylic elastomer composition |
| EP2243770B1 (en) * | 2008-01-30 | 2015-02-25 | Unimatec Co., Ltd. | Novel diurethane compound, process for producing the same, and acrylic rubber composition containing the same |
| JP5509022B2 (en) * | 2010-10-07 | 2014-06-04 | 株式会社オートネットワーク技術研究所 | Ultraviolet curable liquid composition and resin cured product using the same |
| CN103384700B (en) * | 2011-02-28 | 2015-02-11 | Nok株式会社 | Acrylic rubber composition |
| US9217050B2 (en) * | 2012-04-03 | 2015-12-22 | 3M Innovative Properties Company | Crosslinkable composition comprising photobase generators |
| US9528015B2 (en) * | 2012-04-26 | 2016-12-27 | Xerox Corporation | Phase change ink compositions comprising crystalline diurethanes and derivatives thereof |
| CN103059250B (en) | 2013-01-08 | 2014-11-05 | 南开大学 | Novel reversible covalent cross-linked thermoplastic polyurethane |
| EP3202839B1 (en) | 2014-09-29 | 2019-07-24 | Zeon Corporation | Crosslinked rubber |
-
2019
- 2019-11-14 JP JP2020535273A patent/JP6781863B1/en active Active
- 2019-11-14 CN CN201980070284.2A patent/CN112955429B/en active Active
- 2019-11-14 WO PCT/JP2019/044669 patent/WO2020105536A1/en unknown
- 2019-11-14 US US17/295,186 patent/US11932644B2/en active Active
- 2019-11-14 EP EP19886367.2A patent/EP3885338A4/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| US11932644B2 (en) | 2024-03-19 |
| JPWO2020105536A1 (en) | 2021-02-15 |
| EP3885338A4 (en) | 2022-07-13 |
| CN112955429A (en) | 2021-06-11 |
| US20220009934A1 (en) | 2022-01-13 |
| WO2020105536A1 (en) | 2020-05-28 |
| EP3885338A1 (en) | 2021-09-29 |
| CN112955429B (en) | 2022-01-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5240238B2 (en) | Acrylic rubber composition containing diurethane compound | |
| EP3165544B1 (en) | Acrylic rubber, acrylic rubber composition, cross-linked acrylic rubber product, and use of cross-linked acrylic rubber product for seal member | |
| WO2007072900A1 (en) | Crosslinkable rubber composition and rubber crosslinked product | |
| JP5229430B2 (en) | Acrylic rubber composition | |
| EP1739129B1 (en) | Acrylic elastomer composition | |
| EP0905182B1 (en) | Acrylic elastomer composition | |
| JP6781863B1 (en) | New carbamic acid ester compound and acrylic rubber composition containing it | |
| JP3663859B2 (en) | Acrylic elastomer composition | |
| KR20220029573A (en) | Acrylic rubber, acrylic rubber composition, and cross-linked rubber | |
| JP2021191818A (en) | Acrylic rubber composition | |
| EP3438195A1 (en) | Acrylic polymer composition | |
| EP3992236A1 (en) | Acrylic rubber composition and rubber crosslinked product | |
| JP2010241706A (en) | New diurethane compound, method for producing the same and acrylic rubber composition containing the same | |
| CN112236474A (en) | Acrylic elastomer composition | |
| EP3438192A1 (en) | Acrylic polymer composition | |
| EP4310111A1 (en) | Ethylene/(meth)acrylate-based elastomer and production method therefor | |
| JP6385130B2 (en) | Rubber composition and method for improving rubber compression set | |
| US20240158548A1 (en) | Ethylene-(meth)acrylate-based elastomer and method for producing the same | |
| JP2000351884A (en) | Acrylic elastomer composition | |
| EP3438193A1 (en) | Acrylic polymer composition | |
| EP3438191A1 (en) | Acrylic polymer composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20200708 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20200708 |
|
| A871 | Explanation of circumstances concerning accelerated examination |
Free format text: JAPANESE INTERMEDIATE CODE: A871 Effective date: 20200708 |
|
| A975 | Report on accelerated examination |
Free format text: JAPANESE INTERMEDIATE CODE: A971005 Effective date: 20200804 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20200901 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20200911 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20201006 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20201016 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6781863 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |